CN104923290B - A kind of hydrocracking catalyst and its preparation method and application - Google Patents

Abstract

A hydrocracking catalyst and its preparation and application, the catalyst contains a carrier containing Mo-Beta type zeolite molecular sieve, wherein, the n value of the Mo-Beta type zeolite molecular sieve is 0<n<1, n=I/αI ₀ , characterized by FT-IR method, I is the 3610cm ^-1 absorption peak intensity in the FT-IR spectrogram of Mo-Beta type zeolite molecular sieve, I ₀ is the FT-IR of the parent body Beta type zeolite molecular sieve of Mo-Beta type zeolite molecular sieve 3610cm ^-1 absorption peak intensity in the spectrogram, α is the 3740cm-1 absorption peak intensity in the FT-IR spectrum of Mo-Beta type zeolite molecular sieve and the 3740cm ^{- 1} absorption peak intensity in the FT-IR spectrum of parent Beta type zeolite molecular sieve ratio. The preparation method of the molecular sieve comprises: (1) mixing a Beta type molecular sieve with a Mo-containing compound; (2) roasting the mixture obtained in the step (1) in an atmosphere containing water vapor. Compared with the prior art, when the catalyst provided by the invention is used in the hydrocracking reaction of aromatic hydrocarbons, the reactivity of aromatic hydrocarbons, ring opening, selectivity of cracked products and the like are obviously improved.

Description

A kind of hydrocracking catalyst and its preparation method and application

technical field

The invention relates to a hydrogenation treatment catalyst and its preparation method and application.

Background technique

The world's crude oil is developing in the direction of inferior and heavy quality, and one of its characteristics is that the content of aromatics is gradually increasing. In addition to single-ring aromatics in gasoline fractions, high aromatic content is detrimental to product quality or causes processing difficulties. Therefore, how to achieve efficient conversion of aromatics has become the focus and difficulty of research. E.g:

201010609313.9 discloses a catalyst for catalyzing diesel hydrodearomatization. The catalyst is composed of Ni and W and hydrogenation active metal components, modified Y molecular sieve, modified Beta molecular sieve, amorphous silicon aluminum and alumina carrier. The average grain size of modified Y molecular sieve is 100-400nm, the molar ratio of SiO ₂ /Al ₂ O ₃ is 5-40:1, the relative crystallinity is greater than 90%, and the specific surface area is 700-1000m ² /g. Modified Beta molecular sieve The average grain size is 50-200nm, the SiO ₂ /Al ₂ O ₃ molar ratio is 50-200:1, the relative crystallinity is greater than 85%, the specific surface area is 700-900m ² /g, and the treatment of inferior diesel fractions has a high dearomatization rate Greater than 55%.

201180056152.8 discloses a hydrocracking catalyst for preparing valuable light aromatic hydrocarbons from polycyclic aromatic hydrocarbons, the catalyst contains Beta zeolite, pseudo-boehmite and one or more metals selected from Group VIII and Group VIB, And it also contains a co-catalyst component. The catalyst suppresses the generation of naphthenes and paraffins during the conversion of bicyclic aromatics by properly controlling the hydrogenation activity, and at the same time suppresses the hydrogenation saturation of the products benzene, toluene, and xylene (hereinafter referred to as BTX), thereby obtaining high BTX yield.

201110288837.7 discloses a hydrocracking catalyst, which is composed of a hydrogen-active metal, a modified composite molecular sieve and a support composed of amorphous aluminum silicate. The modified composite molecular sieve optimizes the pore distribution and acid distribution of the carrier, and obtains a catalyst carrier with moderate pore size, concentrated pore distribution, developed secondary pores, less acid centers, and moderate acid strength. The catalyst can increase the production of high-quality heavy naphtha.

The key to the efficient conversion of PAHs is how to maximize the conversion of PAHs into high value-added products (ideal components of fuel oil or chemical raw materials). A large number of studies on bicyclic and tricyclic aromatics have shown that the difficulty of conversion is to improve the conversion activity of aromatics, reduce the saturation of aromatics, and improve the selectivity of benzene and alkylbenzenes, especially the selectivity of high value-added products BTX.

Contents of the invention

The technical problem to be solved by the present invention is to provide a hydrocracking catalyst, a preparation method of the catalyst, and an application of the catalyst.

The content of the invention that the present invention relates to comprises:

1. A hydrocracking catalyst containing a carrier containing Mo-Beta zeolite molecular sieve, wherein the n value of the Mo-Beta zeolite molecular sieve is 0<n<1, n=I/αI ₀ , expressed as FT- Characterized by IR method, I is the 3610cm ^-1 absorption peak intensity in the FT-IR spectrum of Mo-Beta type zeolite molecular sieve, and I ₀ is 3610cm in the FT ^- IR spectrum of the parent Beta type zeolite molecular sieve of Mo-Beta type zeolite molecular sieve ¹ Absorption peak intensity, α is the ratio of the 3740cm ^-1 absorption peak intensity in the FT-IR spectrum of the Mo-Beta zeolite molecular sieve to the 3740cm ^-1 absorption peak intensity in the FT-IR spectrum of the parent Beta zeolite molecular sieve.

2. The catalyst according to 1, characterized in that the n value of the Mo-Beta zeolite molecular sieve is 0.3≤n≤0.6.

3. The catalyst according to 1, characterized in that, based on the Mo-Beta zeolite molecular sieve, the molybdenum content calculated as oxide in the Mo-Beta zeolite molecular sieve is 0.5-10% by weight.

4. The catalyst according to 3, characterized in that, based on the Mo-Beta zeolite molecular sieve, the molybdenum content in the Mo-Beta zeolite molecular sieve is 1-6% by weight.

5. The catalyst according to 1, characterized in that the hydrogenation active metal component in the hydrocracking catalyst is selected from at least one Group VIII metal component and at least one VIB metal component, calculated as oxides And based on the catalyst, the content of the Group VIII metal component is 1-10% by weight, and the content of the Group VIB metal component is 5-40% by weight.

6. The catalyst according to 5, characterized in that, the Group VIII metal component is selected from cobalt and/or nickel, and the VIB metal component is selected from molybdenum and/or tungsten, in terms of oxides and the catalyst is Based on this, the content of the Group VIII metal component is 1.5-6% by weight, and the content of the Group VIB metal component is 10-35% by weight.

7. The catalyst according to 1, characterized in that the carrier contains a heat-resistant inorganic oxide matrix, based on the carrier, the content of the heat-resistant inorganic oxide matrix is greater than 0 to less than or equal to 99% by weight %.

8. The catalyst according to 7, characterized in that the heat-resistant inorganic oxide substrate is selected from one or more of alumina, silica and silica-alumina, based on the carrier, the The content of the heat-resistant inorganic oxide matrix is 15-95% by weight.

9. The catalyst according to 1 or 7, characterized in that, based on the catalyst, the content of the carrier in the catalyst is 55-90% by weight, and the content of the Group VIII metal component in terms of oxides is 1-10% by weight, and the content of the Group VIB metal component in terms of oxide is 5-40% by weight.

10. The catalyst according to 9, characterized in that, based on the catalyst, the content of the carrier in the catalyst is 55-85% by weight, and the content of the Group VIII metal component in terms of oxide is 1.5 -6% by weight, the content of the group VIB metal component in terms of oxide is 10-35% by weight.

11. A method for preparing a hydrocracking catalyst, comprising forming and calcining a carrier containing Mo-Beta zeolite molecular sieve, the calcining temperature is 350-700°C, and the calcining time is 1-12 hours, wherein, the The n value of the Mo-Beta type zeolite molecular sieve is 0<n<1, n=I/αI ₀ , characterized by FT-IR method, I is the 3610cm ^-1 absorption in the FT-IR spectrogram of the Mo-Beta type zeolite molecular sieve The intensity of peak, I ₀ is the intensity of 3610cm in the FT-IR spectrogram of the parent Beta zeolite molecular sieve of Mo-Beta type zeolite ^-1 absorption peak intensity, α is 3740cm in the FT-IR spectrogram of Mo-Beta zeolite molecular sieve The ratio of the ^-1 absorption peak intensity to the 3740cm ^-1 absorption peak intensity in the FT-IR spectrum of the parent Beta zeolite molecular sieve.

12. The method according to 11, characterized in that the calcination temperature is 450-650°C and the calcination time is 2-8 hours; the n value of the Mo-Beta zeolite molecular sieve is 0.3≤n≤0.6.

13. The method according to 12, characterized in that, based on the Mo-Beta zeolite molecular sieve, the molybdenum content calculated as oxide in the Mo-Beta zeolite molecular sieve is 0.5-10% by weight.

14. The method according to 13, characterized in that, based on the Mo-Beta zeolite molecular sieve, the molybdenum content calculated as oxide in the Mo-Beta zeolite molecular sieve is 1-6% by weight.

15. The method according to 11, characterized in that the preparation method of the Mo-Beta zeolite molecular sieve comprises: (1) mixing a Beta zeolite molecular sieve with a Mo-containing compound to obtain a Beta zeolite molecular sieve and a Mo-containing compound The mixture of compounds is based on the Mo-Beta zeolite molecular sieve, and the amount of each component is such that in the final Mo-Beta zeolite molecular sieve, the molybdenum content in terms of oxide is 0.5-10% by weight; (2) the step (1) The obtained mixture is treated at a high temperature in an atmosphere containing water vapor, the conditions of the high temperature treatment include a calcination temperature of 200-700°C, a calcination time of 1-24 hours, and a gas flow rate of 0.3-2.0 standard cubic meters containing water vapor m/kg·hour to obtain a Mo-Beta zeolite molecular sieve.

16. The method according to 15, characterized in that, based on the Mo-Beta zeolite molecular sieve, the amount of each component in the step (1) is such that in the final Mo-Beta zeolite molecular sieve, the oxide The calculated molybdenum content is 1-6% by weight; the conditions of the high-temperature treatment in the step (2) include that the calcination temperature is 400-650°C, the calcination time is 2-12 hours, and the gas flow rate containing water vapor is 0.6-1.5 standard Cubic meter/kg·hour.

17. The method according to 15, characterized in that the atmosphere containing water vapor contains diluent gas, wherein the volume mixing ratio of water vapor and diluent gas is 1:10-100.

18. The method according to 17, characterized in that the diluent gas is selected from hydrogen, nitrogen and their mixed gas, or selected from air and a mixed gas of air and nitrogen; the volume mixing ratio of the water vapor to the diluent gas For 1:20-80.

19. The method according to 11, characterized in that the method includes the step of introducing a hydrogenation active metal component into the carrier, and the hydrogenation active metal component in the hydrocracking catalyst is selected from at least A metal component of Group VIII and at least one metal component of VIB, calculated as oxides and based on the catalyst, the introduction amount of metal component of Group VIII makes the content of metal component of Group VIII in the final catalyst be 1-10% by weight, the introduction amount of the Group VIB metal component makes the content of the Group VIB metal component in the final catalyst 5-40% by weight.

20. The method according to 19, characterized in that the Group VIII metal component is selected from cobalt and/or nickel, and the VIB metal component is selected from molybdenum and/or tungsten, calculated as oxides and based on the catalyst Standard, the introduction amount of the Group VIII metal component makes the content of the Group VIII metal component in the final catalyst be 1.5-6% by weight, and the introduction amount of the VIB Group metal component makes the content of the VIB Group metal component in the final catalyst The content is 10-35% by weight.

21. The method according to 11, characterized in that the method includes the step of introducing a heat-resistant inorganic oxide matrix into the carrier, based on the carrier, the introduction of the heat-resistant inorganic oxide matrix The amount is such that the content of the refractory inorganic oxide matrix in the final support is greater than 0 to less than or equal to 99% by weight.

22. The method according to 21, characterized in that, based on the carrier, the introduction amount of the heat-resistant inorganic oxide matrix is such that the content of the heat-resistant inorganic oxide matrix in the final carrier is 15-95% by weight.

23. A hydrocracking method, comprising contacting hydrocarbon oil with a catalyst under hydrocracking conditions, wherein the catalyst is the catalyst provided in 1-10 above.

The 3610cm ^-1 absorption peak in the FT-IR spectrum of the Beta zeolite refers to the absorption peak at 3610 ± 10cm ^-1 in the FT-IR spectrum, and this absorption peak belongs to the vibration absorption peak of the acidic hydroxyl group of the Beta zeolite . The 3740cm ^-1 absorption peak in the FT-IR spectrum of the Beta zeolite refers to the absorption peak at 3740cm ^-1 ±10cm ^-1 in the FT-IR spectrum, which belongs to the Beta-type zeolite Si-OH Vibration absorption peak.

The inventors of the present invention have found that when the Beta-type zeolite molecular sieve is introduced into the Mo metal component by n=I/αI ₀ , when the 3610cm ^-1 absorption peak intensity in the FT-IR spectrogram is changed, the method prepared by the present invention is adopted. The intensity of the vibration characteristic absorption peak of the acidic hydroxyl group of the Mo-Beta type zeolite molecular sieve is reduced. However, the catalyst prepared by using the Mo-Beta zeolite molecular sieve has significantly improved hydrogenation aromatics saturation ring opening and cracking performance.

In the present invention, the Mo-Beta zeolite is a Beta type zeolite with 0<n<1, preferably 0.3≤n≤0.6. Preferably, the Mo-Beta type zeolite molecular sieve is used as a benchmark (in the present invention, the content (mass fraction) of molybdenum oxide in the Mo-Beta type zeolite molecular sieve=the measured value/molybdenum oxide in the Mo-Beta type zeolite molecular sieve to be tested (the amount of the Mo-Beta type zeolite molecular sieve to be tested × dry basis). The dry basis is the ratio of the weight of the sample to be tested after roasting at 600 ° C for 4 hours in an air atmosphere to the weight before roasting), and the Mo in the Mo-Beta zeolite The content is 0.5-10% by weight, more preferably 1-6% by weight.

The method of introducing Mo to Beta type zeolite molecular sieve of the present invention comprises:

(1) Mixing Beta-type zeolite molecular sieves with Mo-containing compounds to obtain a mixture of Beta-type zeolite molecular sieves and Mo-containing compounds;

(2) Calcining the mixture obtained in step (1) in an atmosphere containing water vapor to obtain a Mo-Beta zeolite molecular sieve;

Wherein, based on the Mo-Beta zeolite molecular sieve on a dry basis, the amount of each component in the step (1) is such that in the final Mo-Beta zeolite molecular sieve, the molybdenum content in terms of oxides is preferably 0.5 -10% by weight, further preferably the molybdenum content in terms of oxides is 1-6% by weight; the molybdenum-containing compound is preferably selected from molybdenum oxides, chlorides or molybdates; the roasting in the step (2) The conditions include: the temperature is 200-700°C, preferably 400-650°C, the time is 1-24 hours, preferably 3-12 hours, the gas flow rate containing water vapor is 0.3-2 standard cubic meters/kg·hour, preferably 0.6-1.5 Nm3/kg·h.

In the aforementioned method, it is preferred that the atmosphere containing water vapor contains a diluent gas, and the diluent gas can be selected from examples such as: selected from hydrogen, nitrogen and their mixtures, or selected from air and a mixture of air and nitrogen, wherein, The volume mixing ratio of the water vapor and the diluent gas is preferably 1:10-100, more preferably 1:20-80.

The catalyst provided according to the present invention preferably contains a refractory inorganic oxide. The heat-resistant inorganic oxide can be selected from any carrier (or matrix) commonly used in the preparation of hydrogenation catalysts. In a preferred embodiment, the heat-resistant inorganic oxide is selected from one or more of alumina, silica and silica-alumina. They can be commercially available or obtained by any existing method.

According to the catalyst provided by the present invention, the carrier can be made into various easy-to-handle moldings, such as microspheres, spheres, tablets or strips, etc. depending on different requirements. The molding can be carried out by conventional methods, for example, the Mo-Beta zeolite molecular sieve, with or without heat-resistant inorganic oxide, is prepared by extrusion molding and roasting. When the carrier is extruded, an appropriate amount of extrusion aid and/or adhesive can be added to the carrier, and then extruded. The type and amount of the extrusion aid and the peptizing agent are well known to those skilled in the art, for example, the common extrusion aid can be selected from one of squash powder, methyl cellulose, starch, polyvinyl alcohol, polyethanol or several.

Catalysts according to the present invention are provided in which the hydrogenation-active metal component is selected conventionally for such catalysts, for example, comprising at least one metal component selected from Group VIII and at least one metal component selected from Group VIB. Preferred Group VIII metal components are cobalt and/or nickel and Group VIB metal components are molybdenum and/or tungsten. In terms of oxides and based on the catalyst, the content of the Group VIII metal component is preferably 1-10% by weight, more preferably 1.5-6% by weight, and the content of the Group VIB metal component is preferably 5% by weight. -40% by weight, more preferably 10-35% by weight. The present invention includes Mo in the Mo-Beta zeolite molecular sieve when calculating the content of the VIB group metal component.

On the premise that it is sufficient to load the hydrogenation active metal component on the carrier, the present invention has no special limitation on the loading method, and the preferred method is the impregnation method, including the impregnation of preparing the compound containing the metal solution, which is then used to impregnate the carrier. The impregnation method is a conventional method, for example, it may be impregnation with excess liquid or pore saturation method. Wherein, a specified content of the catalyst can be prepared by adjusting and controlling the concentration and amount of the solution containing the metal component or the amount of the carrier, which is easily understood and realized by those skilled in the art.

The metal component compound selected from group VIB is selected from one or more of the soluble compounds in them, such as one or more of molybdenum oxide, molybdate, paramolybdate, preferably among them Molybdenum oxide, ammonium molybdate, ammonium paramolybdate; one or more of tungstate, metatungstate, ethyl metatungstate, preferably ammonium metatungstate, ethyl ammonium metatungstate . The compound containing metal components selected from Group VIII is selected from one or more of their soluble compounds, such as cobalt nitrate, cobalt acetate, basic cobalt carbonate, cobalt chloride and cobalt soluble complexes One or more, preferably cobalt nitrate, basic cobalt carbonate; one or more of nickel nitrate, nickel acetate, basic nickel carbonate, nickel chloride and nickel soluble complexes, preferably nickel nitrate , Basic nickel carbonate.

The catalyst provided by the present invention may also contain any material that does not affect the catalytic performance of the catalyst provided by the present invention or that can improve the catalytic performance of the catalyst provided by the present invention. For example, one or two of the components such as phosphorus and titanium can be introduced, calculated as elements and based on the catalyst, the introduction amount of the above additives is 0-10% by weight, preferably 0.5-5% by weight.

When the catalyst also contains one or two components selected from components such as phosphorus, titanium or silicon, the introduction method of the components selected from phosphorus, titanium and the like is a conventional method, such as including The compound of the auxiliary agent is directly mixed with the solid acid component and pseudo-boehmite, shaped and roasted; it can be mixed with the compound containing the auxiliary agent and the compound containing the hydrogenation active metal component after preparing a mixed solution The carrier is contacted; it can also be that the compound containing the auxiliary agent is separately prepared into a solution, then contacted with the carrier and calcined. When the auxiliary agent and the hydrogenation active metal are respectively introduced into the carrier, it is preferable to first contact the carrier with a solution containing the auxiliary agent compound and roast it, and then contact it with the solution containing the compound of the hydrogenation active metal component, for example, by impregnating method, the calcination temperature is 250-600°C, preferably 350-500°C, and the calcination time is 2-8 hours, preferably 3-6 hours.

According to the present invention, after the metal impregnation step is completed, steps such as drying, calcination or non-calcination may be carried out as required. The conditions of the drying and calcination are conventional, for example, the drying temperature is 100-300°C, preferably 100-280°C, and the drying time is 1-12 hours, preferably 2-8 hours; the calcination temperature is 350-550°C. °C, preferably 400-500 °C, and the firing time is 1-10 hours, preferably 2-8 hours.

The catalyst provided by the invention can also contain one or more organic compounds selected from oxygen-containing or nitrogen-containing organic compounds, and preferred oxygen-containing organic compounds are selected from one or more of organic alcohols and organic acids; preferably The nitrogen-containing organic compound is selected from one or more of organic amines. Examples of oxygen-containing organic compounds include ethylene glycol, glycerol, polyethylene glycol (molecular weight: 200-1500), diethylene glycol, butanediol, acetic acid, maleic acid, oxalic acid, aminotriacetic acid, One or more of 1,2-cyclohexanediaminetetraacetic acid, citric acid, tartaric acid and malic acid, and the nitrogen-containing organic compound can be ethylenediamine, EDTA and its ammonium salts. The molar ratio of the organic compound to the sum of Group VIII and Group VIB metal components calculated as oxides is 0.03-2, preferably 0.08-1.5.

According to conventional methods in this field, before use, the hydrotreating catalyst can be presulfurized with sulfur, hydrogen sulfide or sulfur-containing raw materials at a temperature of 140-370° C. in the presence of hydrogen, such presulfurization It can be vulcanized outside or in-situ, and the active metal components supported by it can be converted into metal sulfide components.

In the hydrocracking method provided by the present invention, there are no special restrictions on the conditions of the hydrocracking reaction, and common reaction conditions can be used, for example, the reaction temperature is 200-420°C, more preferably 220- 400°C, the pressure is 2-18 MPa, more preferably 2-15 MPa, the liquid hourly space velocity is 0.3-10 hours ^-1 , more preferably 0.3-5 hours ^-1 , the hydrogen-oil volume ratio is 50-5000, further Preferably 50-4000.

The device for the hydroprocessing reaction can be carried out in any reaction device sufficient to allow the feed oil to contact the catalyst under the hydroprocessing reaction conditions, for example, in the fixed bed reactor, moving bed reaction in reactors or ebullating bed reactors.

Compared with the prior art, when the catalyst is used in the hydrocracking reaction process, the invention provides the advantages of low aromatic content in the diesel distillate oil, high cetane number and increased production of high-quality gasoline distillates. It can be directly used to process various hydrocarbon oil raw materials for hydrogenation upgrading. The hydrocarbon oil raw materials include various heavy mineral oils or synthetic oils or their mixed distillates, for example, selected from crude oil, distillate oil, solvent refined oil, wax paste, wax bottom oil, Fischer-Tropsch synthetic oil, coal liquefied oil One or more of light deasphalted oil and heavy deasphalted oil. It is especially suitable for hydrocracking or hydro-upgrading of low-quality diesel oil.

Detailed ways

The following examples will further illustrate the present invention.

The hydroxyl group of the molecular sieve framework was measured by Fourier transform infrared (FT-IR). Firstly, the sample was calcined at 350°C for 2 hours, and the vacuum degree was kept at 10 ^-6 Pa. Then, the hydroxyl group infrared spectrum of the molecular sieve was measured at room temperature. The Mo content in the MoY molecular sieve is measured by X-ray fluorescence spectrometry (XRF). The experimental method is that the molecular sieve sample is pressed into tablets, rhodium target, laser voltage 50kV, laser current 50mA, and external standard method is used for semi-quantitative analysis.

Example 1

Take 200.0 g of Beta molecular sieve (product of Changling Catalyst Branch Company, dry basis 0.81) and 0.8 g of molybdenum trioxide, grind them in a mortar and mix them evenly. Then put it in the constant temperature zone of the tube furnace, and bake it at 300°C for 24 hours under the atmosphere of hydrogen and water vapor, the gas flow rate is 0.5m ³ /(kg·h), and the mixing ratio of water vapor and hydrogen is 1:40. The obtained Mo-modified Beta-type molecular sieve Mo-Beta1 was determined by XRF method (the same below). The content of MoO ₃ in Mo-Beta1 and its n value are listed in Table 1.

Mix 200.0 grams of pseudo-boehmite (product of Changling Catalyst Branch, dry basis 0.71) with 176.0 grams of Mo-Beta1 sample, extrude into a clover-shaped strip with a circumscribed circle diameter of 1.6 mm, and dry the wet strip at 150°C for 3 hours. Calcined at 550°C for 3h to obtain carrier Z1.

Take 100.2 grams of carrier Z1, impregnate with 95 ml of a mixed solution containing MoO ₃ 182.1 g/L, NiO78.9 g/L ammonium heptamolybdate and nickel nitrate for 4 hours, dry at 150°C for 3 hours, and bake at 400°C for 3 hours to obtain Catalyst C1. Based on the catalyst, the composition of the C1 catalyst after calcination is shown in Table 2 (the active metal component was determined by XRF method, the same below).

Example 2

Take 200.0 grams of Beta molecular sieve (product of Changling Catalyst Branch Company, dry basis 0.81) and 8.5 grams of molybdenum trioxide, grind them in a mortar, and mix them evenly. Then put it in the constant temperature zone of the tube furnace, and bake it at 450°C for 4 hours under the atmosphere of hydrogen and water vapor. The gas flow rate is 0.8m ³ /(kg·h), and the mixing ratio of water vapor and hydrogen is 1:30. The Mo-modified Beta molecular sieve Mo-Beta2 was obtained. _The content of MoO3 in Mo-Beta2 and its n value are listed in Table 1.

Mix 200.0 grams of pseudo-boehmite (product of Changling Catalyst Branch, dry basis 0.71) with 45.7 grams of Mo-Beta2 sample, extrude into a clover-shaped strip with a circumcircle diameter of 1.6 mm, and dry the wet strip at 150°C for 3 hours. Calcined at 550°C for 3h to obtain carrier Z2.

Take 101.0 grams of carrier Z2, impregnate with 78 milliliters of nickel and molybdenum complex solution containing MoO ₃ 648.9 g/L, NiO 128.2 g/L, P ₂ O ₅ 64.1 g/L, 138.5 g/L citric acid for 4 hours, Dry at 150°C for 3 hours to obtain catalyst C2. Based on the catalyst, the composition of the C2 catalyst after calcination is shown in Table 2.

Example 3

Mix 200.0 grams of pseudo-boehmite (product of Changling Catalyst Branch, dry basis 0.71) with 98.4 grams of Mo-Beta2 sample, extrude into a clover-shaped strip with a circumcircle diameter of 1.6 mm, and dry the wet strip at 150 °C for 3 hours. Calcined at 550°C for 3h to obtain carrier Z3.

Take 101.8 grams of carrier Z3, impregnate with 90 milliliters of nickel and molybdenum complex solution containing MoO3 276.3 g/L, _NiO44.4 g/L, _P2O5 29.7 g/L, 48.0 g/L citric acid for ₄ hours, Dry at 150°C for 3 hours to obtain catalyst C3. Based on the catalyst, the composition of the C3 catalyst after calcination is shown in Table 2.

Example 4

Take 200.0 grams of Beta molecular sieve (product of Changling Catalyst Branch Company, dry basis 0.81) and 8.5 grams of molybdenum trioxide, grind them in a mortar, and mix them evenly. Then put it in the constant temperature zone of the tube furnace, and bake it at 550°C for 2 hours under the atmosphere of hydrogen and water vapor. The gas flow rate is 1.2m ³ /(kg·h), and the mixing ratio of water vapor and hydrogen is 1:50. The Mo-modified Beta-type molecular sieve Mo-Beta3 was obtained, and the content of MoO ₃ in Mo-Beta3 and its n value are listed in Table 1.

Mix 200.0 grams of pseudo-boehmite (product of Changling Catalyst Branch, dry basis 0.71) with 98.4 grams of Mo-Beta3 sample, extrude into a clover-shaped strip with a circumcircle diameter of 1.6 mm, and dry the wet strip at 150 ° C for 3 hours. Calcined at 550°C for 3h to obtain carrier Z4.

Take 101.8 grams of carrier Z4, impregnate with 90 milliliters of nickel and molybdenum complex solution containing MoO3 276.3 g/L, _NiO44.4 g/L, _P2O5 29.7 g/L, 48.0 g/L citric acid for ₄ hours, Dry at 150°C for 3 hours to obtain catalyst C4. Based on the catalyst, the composition of the C4 catalyst after calcination is shown in Table 2.

Example 5

Mix 200.0 grams of pseudo-boehmite (product of Changling Catalyst Branch, dry basis 0.71) with 78.3 grams of Mo-Beta3 sample, extrude into a cylindrical strip with a circumscribed circle diameter of 1.6 mm, and dry the wet strip at 150 ° C for 3 hours. Calcined at 550°C for 3 hours to obtain carrier Z5.

Take 101.6 grams of carrier Z5, impregnate with 85 milliliters of nickel and molybdenum complex solution containing MoO ₃ 589.0 g/L, NiO 117.6 g/L, P ₂ O ₅ 58.8 g/L, and 127.1 g/L citric acid for 4 hours, Dry at 150°C for 3 hours to obtain catalyst C5. Based on the catalyst, the composition of the C5 catalyst after calcination is shown in Table 2.

Example 6

Take 200.0 grams of Beta molecular sieve (product of Changling Catalyst Branch Company, dry basis 0.81) and 14.1 grams of molybdenum trioxide, grind them in a mortar, and mix them evenly. Then put it in the constant temperature zone of the tube furnace, and bake it at 600°C for 8 hours under the atmosphere of hydrogen and water vapor, the gas flow rate is 1.8m ³ /(kg·h), and the mixing ratio of water vapor and hydrogen is 1:90. The Mo-modified Beta molecular sieve Mo-Beta4 was obtained, and the content of MoO3 in Mo _- Beta4 and its n value are listed in Table 1.

Mix 200.0 grams of pseudo-boehmite (product of Changling Catalyst Branch Company, dry basis 0.71) with 101.0 grams of Mo-Beta4 sample, extrude into clover-shaped strips with a circumcircle diameter of 1.6 mm, and dry the wet strips at 150°C for 3 hours. Calcined at 550°C for 3h to obtain carrier Z6.

Take 103.0 grams of carrier Z6, impregnate with 85 milliliters of nickel and molybdenum complex solution containing MoO3 278.4 g/L, _NiO47.1 g/L, _P2O5 31.4 g/L, 50.8 g/L citric acid for ₄ hours, Dry at 150°C for 3 hours to obtain catalyst C6. Based on the catalyst, the composition of the C6 catalyst after calcination is shown in Table 2.

Example 7

Take 200.0 grams of Beta molecular sieve (product of Changling Catalyst Branch Company, dry basis 0.81) and 14.1 grams of molybdenum trioxide, grind them in a mortar, and mix them evenly. Then put it in the constant temperature zone of the tube furnace, and bake it at 600°C for 8 hours under the atmosphere of hydrogen and water vapor, the gas flow rate is 0.8m ³ /(kg·h), and the mixing ratio of water vapor and hydrogen is 1:30. The Mo-modified Beta-type molecular sieve Mo-Beta5 was obtained, and the content of MoO ₃ in Mo-Beta5 and its n value are listed in Table 1.

Mix 200.0 grams of pseudo-boehmite (product of Changling Catalyst Branch, dry basis 0.71), 46.7 grams of silica-alumina (product of Changling Catalyst Branch, dry basis 76%) and 78.1 grams of Mo-Beta5 samples, Extruded into a clover-shaped bar with a circumscribed circle diameter of 1.6 mm, the wet bar was dried at 150°C for 3 hours, and then calcined at 550°C for 3 hours to obtain carrier Z7.

Take 102.2 grams of carrier Z7, impregnate with 85 ml of a mixed solution containing MoO ₃ 180.0 g/L, NiO8.2 g/L ammonium heptamolybdate and nickel nitrate for 4 hours, dry at 150°C for 3 hours, and bake at 400°C for 3 hours to obtain Catalyst C7. Based on the catalyst, the composition of the C7 catalyst after calcination is shown in Table 2.

Example 8

Take 200.0 g of Mo-Beta2 molecular sieve, press it on a DY-20 powder tablet press, press at 10 MPa, and dry at 150° C. for 3 hours to prepare carrier Z8.

Take 105.3 grams of Z8, impregnate with 75 milliliters of nickel and molybdenum complex solution containing MoO ₃ 285.4 g/L, NiO 40 g/L, P2O5 26.7 g/L, 43.2 g/L citric acid for 4 hours, and dry at 150°C for 3 hours. hours, the catalyst C8 was obtained. Based on the catalyst, the composition of the C8 catalyst after calcination is shown in Table 2.

Example 9

Take 200.0 grams of Beta molecular sieve (product of Changling Catalyst Branch Company, dry basis 0.81) and 14.1 grams of molybdenum trioxide, grind them in a mortar, and mix them evenly. Then put it in the constant temperature zone of the tube furnace, and bake it at 300°C for 12 hours under the atmosphere of air and water vapor. The gas flow rate is 1.2m ³ /(kg·h), and the mixing ratio of water vapor and air is 1:15. The obtained Mo-modified Beta molecular sieve Mo- _Beta6 , the content of MoO3 in Mo-Beta6 and its n value are listed in Table 1.

Mix 200.0 grams of pseudo-boehmite (product of Changling Catalyst Branch, dry basis 0.71) with 125.1 grams of Mo-Beta6 sample, extrude into cylindrical strips with a diameter of 1.6 mm, and dry the wet strips at 150°C for 3 hours, 550 It was calcined at ℃ for 3h to obtain carrier Z9.

Take 103.5 grams of carrier Z9, impregnate with 85 ml of a mixed solution containing MoO ₃ 164.7 g/L, NiO8.2 g/L ammonium heptamolybdate and nickel nitrate for 4 hours, dry at 150°C for 3 hours, and bake at 400°C for 3 hours to obtain Catalyst C9. Based on the catalyst, the composition of the C9 catalyst after calcination is shown in Table 2.

Example 10

Take 200.0 grams of Beta molecular sieve (product of Changling Catalyst Branch Company, dry basis 0.81) and 26.8 grams of molybdenum pentachloride, grind them in a mortar and mix them evenly. Then put it in the constant temperature zone of the tube furnace, and bake it at 300°C for 24 hours under the atmosphere of nitrogen and water vapor. The gas flow rate is 1.2m ³ /(kg·h), and the mixing ratio of water vapor and nitrogen is 1:15. The Mo-modified Beta molecular sieve Mo-Beta7 was obtained, and the content of MoO ₃ in Mo-Beta7 and its n value are listed in Table 1.

Mix 200.0 grams of pseudo-boehmite (product of Changling Catalyst Branch Company, dry basis 0.71) with 125.1 grams of Mo-Beta7 sample, extrude into cylindrical strips with a diameter of 1.6 mm, and dry the wet strips at 150 ° C for 3 hours, 550 It was calcined at ℃ for 3h to obtain carrier Z10.

Take 103.5 grams of carrier Z10, impregnate with 85 ml of a mixed solution containing MoO ₃ 164.7 g/L, NiO8.2 g/L ammonium heptamolybdate and nickel nitrate for 4 hours, dry at 150°C for 3 hours, and bake at 400°C for 3 hours to obtain Catalyst C10. Based on the catalyst, the composition of the C10 catalyst after calcination is shown in Table 2.

Example 11

Take 200.0 grams of Beta molecular sieve (product of Changling Catalyst Branch Company, dry basis 0.81) and 14.1 grams of molybdenum trioxide, grind them in a mortar, and mix them evenly. Then put it in the constant temperature zone of the tube furnace, and bake it at 300°C for 8 hours under the water vapor atmosphere, and the gas flow rate in it is 0.4m ³ /(kg·h). The Mo-modified Beta molecular sieve Mo-Beta8 was obtained. _The content of MoO3 in Mo-Beta8 and its n value are listed in Table 1.

Mix 200.0 grams of pseudo-boehmite (product of Changling Catalyst Branch Company, dry basis 0.71) with 125.1 grams of Mo-Beta8 sample, extrude into cylindrical strips with a diameter of 1.6 mm, and dry the wet strips at 150 ° C for 3 hours, 550 It was calcined at ℃ for 3h to obtain carrier Z11.

Take 103.5 grams of carrier Z11, impregnate with 85 ml of a mixed solution containing MoO ₃ 164.7 g/L, NiO8.2 g/L ammonium heptamolybdate and nickel nitrate for 4 hours, dry at 150°C for 3 hours, and bake at 400°C for 3 hours to obtain Catalyst C11. Based on the catalyst, the composition of the C11 catalyst after calcination is shown in Table 2.

Comparative example 1

Mix 200.0 grams of pseudo-boehmite (product of Changling Catalyst Branch, dry basis 0.71) with 94.4 grams of Beta molecular sieve (product of Changling Catalyst Branch, dry basis 0.81), and extrude into a clover shape with a circumscribed circle diameter of 1.6 mm Strips, wet strips were dried at 150°C for 3 hours and calcined at 550°C for 3 hours to obtain carrier DZ1.

Take 100.0 grams of carrier DZ1, impregnate with 90 milliliters of nickel and molybdenum complex solution containing MoO ₃ 370.4 g/L, NiO4 4.4 g/L, P ₂ O ₅ 29.7 g/L, 48.0 g/L citric acid for 4 hours, Dry at 150°C for 3 hours to obtain catalyst DC1. Based on the catalyst, the composition of the DC1 catalyst after calcination is shown in Table 2.

Table 1 Composition information of modified molecular sieves

Table 2 Composition information of supports and catalysts

Examples 12-14

The following examples illustrate the performance of the catalysts provided by the present invention.

Using tetralin with a purity of 99% as raw material (analytically pure), evaluate the tetralin reaction performance of catalysts C3, C4, and C6 provided by the invention on a micro-fixed bed. The catalyst loading is 1.0 grams, and the reaction conditions are 330 ° C to 390°C, pressure 4.0MPa. For better comparison, the following two performance indicators are given and defined, and the results are listed in Table 3.

Comparative example 2

DC1 was evaluated by the same method as in Examples 12-14, and the results are listed in Table 3.

Table 3 Catalyst tetralin hydrocracking evaluation results

The results in Table 3 show that, compared with the comparative catalyst DC1: the relative conversion rate of the patented tetralin provided by the present invention is increased by 12% to 40%; under the same conversion rate, the relative BTX selectivity is increased by 18% to 38%.

Claims (21)

1. a kind of hydrocracking catalyst, the carrier containing the zeolite molecular sieve of type containing Mo-Beta, with the Mo-Beta types zeolite On the basis of molecular sieve, the content for the molybdenum counted in the Mo-Beta types zeolite molecular sieve using oxide as 0.5-10 weight %, wherein, The Mo-Beta types zeolite molecular sievenIt is worth for 0<n <1,n=I/αI₀, characterized in FT-IR methods, I is Mo-Beta types 3610cm in the FT-IR spectrograms of zeolite molecular sieve^-1Absorption peak strength, I₀For the parent Beta types of Mo-Beta type zeolite molecular sieves 3610cm in the FT-IR spectrograms of zeolite molecular sieve^-1Absorption peak strength,αIn FT-IR spectrograms for Mo-Beta type zeolite molecular sieves 3740cm^-1Absorption peak strength and 3740cm in the FT-IR spectrograms of parent Beta type zeolite molecular sieves^-1The ratio of absorption peak strength.

2. catalyst according to claim 1, it is characterised in that the Mo-Beta types zeolite molecular sievenIt is worth for 0.3 ≤n≤0.6。

3. catalyst according to claim 1, it is characterised in that on the basis of the Mo-Beta types zeolite molecular sieve, institute The content for the molybdenum counted in Mo-Beta type zeolite molecular sieves using oxide is stated as 1-6 weight %.

4. catalyst according to claim 1, it is characterised in that the hydrogenation active metals in the hydrocracking catalyst Component is selected from least one metal component of group VIII and at least one metal component of group VIB, is urged in terms of oxide and with described On the basis of agent, the content of the metal component of group VIII is 1-10 weight %, and the content of metal component of group VIB is 5-40 weights Measure %.

5. catalyst according to claim 4, it is characterised in that the metal component of group VIII is selected from cobalt and/or nickel, the VI B races metal component is selected from molybdenum and/or tungsten, is counted by oxide and on the basis of the catalyst, the metal component of group VIII Content be 1.5-6 weight %, the content of metal component of group VIB is 10-35 weight %.

6. catalyst according to claim 1, it is characterised in that contain heat-resistant inorganic oxide matrix in the carrier, On the basis of the carrier, the content of the heat-resistant inorganic oxide matrix is to less than or equal to 99 weight % more than 0.

7. catalyst according to claim 6, it is characterised in that the heat-resistant inorganic oxide matrix be selected from aluminum oxide, One or more in silica and silica-alumina, on the basis of the carrier, the heat-resistant inorganic oxide matrix Content is 15-95 weight %.

8. catalyst according to claim 4, it is characterised in that on the basis of the catalyst, carried in the catalyst The content of body is 55-90 weight %, and the content for the metal component of group VIII counted using oxide is 1-10 weight %, with oxidation The content of the metal component of group VIB of thing meter is 5-40 weight %.

9. catalyst according to claim 8, it is characterised in that on the basis of the catalyst, carried in the catalyst The content of body is 55-85 weight %, and the content for the metal component of group VIII counted using oxide is 1.5-6 weight %, with oxidation The content of the metal component of group VIB of thing meter is 10-35 weight %.

10. a kind of preparation method of hydrocracking catalyst, including prepare the zeolite molecular sieve of type containing Mo-Beta through being molded and being calcined Carrier, the temperature of the roasting is 350-700 DEG C, and roasting time is 1-12 hours, with the Mo-Beta types zeolite molecular sieve On the basis of, the content for the molybdenum counted in the Mo-Beta zeolite molecular sieves using oxide as 0.5-10 weight %, wherein, the Mo- Beta type zeolite molecular sievesnIt is worth for 0<n <1,n=I/αI₀, characterized in FT-IR methods, I is Mo-Beta type zeolite molecules 3610cm in the FT-IR spectrograms of sieve^-1The intensity of absworption peak, I₀For the parent Beta types zeolite point of Mo-Beta type zeolite molecular sieves 3610cm in the FT-IR spectrograms of son sieve^-1The intensity of absworption peak,αIn FT-IR spectrograms for Mo-Beta type zeolite molecular sieves 3740cm^-1Absorption peak strength and 3740cm in the FT-IR spectrograms of parent Beta type zeolite molecular sieves^-1The ratio of absorption peak strength.

11. according to the method for claim 10, it is characterised in that the temperature of the roasting is 450-650 DEG C, roasting time For 2-8 hours；The Mo-Beta types zeolite molecular sievenBe worth for 0.3≤n≤0.6。

12. according to the method for claim 10, it is characterised in that on the basis of the Mo-Beta types zeolite molecular sieve, institute The content for the molybdenum counted in Mo-Beta type zeolite molecular sieves using oxide is stated as 1-6 weight %.

13. according to the method for claim 10, it is characterised in that the preparation method of the Mo-Beta types zeolite molecular sieve Including：（1）Beta types zeolite molecular sieve is mixed with compound containing Mo, obtains a kind of Beta types zeolite molecular sieve and chemical combination containing Mo The mixture of thing, on the basis of the Mo-Beta types zeolite molecular sieve, the dosage of each component makes final Mo-Beta types zeolite point In son sieve, using the molybdenum content that oxide is counted as 0.5-10 weight %；（2）By step（1）Obtained mixture is in steam-laden gas High-temperature process under atmosphere, it is 200-700 DEG C that the condition of the high-temperature process, which includes sintering temperature, and roasting time is 1-24 hours, Steam-laden gas flow is 0.3-2 standard cubic meters/kilogram hour, obtains Mo-Beta type zeolite molecular sieves.

14. according to the method for claim 13, it is characterised in that on the basis of the Mo-Beta types zeolite molecular sieve, institute State step（1）The dosage of middle each component makes in final Mo-Beta types zeolite molecular sieve, using the molybdenum content that oxide is counted as 1-6 weights Measure %；The step（2）In high-temperature process condition include sintering temperature be 400-650 DEG C, roasting time is 2-12 hours, Steam-laden gas flow is 0.6-1.5 standard cubic meters/kilogram hour.

15. according to the method for claim 13, it is characterised in that contain diluent gas in the steam-laden atmosphere, Wherein, the volume mixture ratio of the vapor and diluent gas is 1：10-100.

16. according to the method for claim 15, it is characterised in that the diluent gas is selected from hydrogen, nitrogen and its mixing Gas, or the gaseous mixture selected from air and air and nitrogen；The volume mixture ratio of the vapor and diluent gas is 1： 20-80。

17. according to the method for claim 10, it is characterised in that methods described includes introducing hydrogenation into the carrier The step of active metal component, the hydrogenation active metal component in the hydrocracking catalyst are selected from least one VIIIth race gold Belong to component and at least one metal component of group VIB, counted by oxide and on the basis of the catalyst, the group VIII metal The introduction volume of component makes the content of metal component of group VIII in final catalyst be 1-10 weight %, the metal component of group VIB Introduction volume make the content of metal component of group VIB in final catalyst be 5-40 weight %.

18. according to the method for claim 17, it is characterised in that the metal component of group VIII is selected from cobalt and/or nickel, the VI B races metal component is selected from molybdenum and/or tungsten, is counted by oxide and on the basis of the catalyst, the metal component of group VIII Introduction volume make the content of metal component of group VIII in final catalyst be 1.5-6 weight %, the metal component of group VIB Introduction volume makes the content of metal component of group VIB in final catalyst be 10-35 weight %.

19. according to the method for claim 10, it is characterised in that methods described includes introducing into the carrier heat-resisting The step of inorganic oxide matrix, on the basis of the carrier, the introduction volume of the heat-resistant inorganic oxide matrix makes finally to carry The content of heat-resistant inorganic oxide matrix is to less than or equal to 99 weight % more than 0 in body.

20. according to the method for claim 19, it is characterised in that on the basis of the carrier, the heat resistant inorganic oxidation The introduction volume of thing matrix makes the content of heat-resistant inorganic oxide matrix in final carrier be 15-95 weight %.

21. a kind of method for hydrogen cracking, it is included under hydrocracking condition and contacts hydrocarbon ils with catalyst, wherein, the catalysis Agent is the catalyst that preceding claims 1-9 is provided.